Titanium oxide nanotubes were prepared by hydrothermal treatment of TiO2 powder in NaOH aqueous solution and subsequently calcined. Titanium oxide nanotubes were further decorated by TiO2 nanoparticles through in situ hydrolysis of titanium isopropoxide containing alcohol and ammonia in an aqueous medium to form the composite catalyst (TNP/TiO2NTs). The morphology and structure of TNP/TiO2NTs were characterized by scanning and transmission electron microscopy, X-ray diffraction, UV-Vis, and Raman spectra. The separation efficiency of photo-excited carriers was investigated by photoluminescence technique and photoelectrochemical behavior. The photocatalytic activity was evaluated by the photocatalytic degradation of methyl orange. Due to the synergy effect caused by the interaction of titanium oxide nanotubes and TiO2 nanoparticles, the TNP/TiO2NTs composite shows efficient photogenerated carriers' separation and the increased light absorption. The photocatalytic activity was enhanced.